CN109813792B - Quantitative method for sample detection by using ion mobility spectrometry - Google Patents
Quantitative method for sample detection by using ion mobility spectrometry Download PDFInfo
- Publication number
- CN109813792B CN109813792B CN201711161879.8A CN201711161879A CN109813792B CN 109813792 B CN109813792 B CN 109813792B CN 201711161879 A CN201711161879 A CN 201711161879A CN 109813792 B CN109813792 B CN 109813792B
- Authority
- CN
- China
- Prior art keywords
- sample
- signal intensity
- ion
- concentration
- samples
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention discloses a quantitative method for sample detection by ion mobility spectrometry, which tracks the signal intensity of the ion peak value of a sample product in the sample introduction process and uses the maximum signal intensity of the sample in the sample introduction process and the signal intensity of the initial reaction reagent ion as the signal intensityObtaining the average proportionality coefficient of the sample under different concentrations, fitting according to a second-order reaction kinetic formula of the sample and the reagent ions to obtain a quantitative curve of the sample, taking propofol in exhaled breath as an example, and establishing a standard curve equation of ion mobility spectrometry between the concentration of the exhaled breath propofol of 1-40ppbv
Coefficient of correlation R2The quantitative method corrects the change of the signal intensity of the sample caused by the change of the signal intensity of the initial reaction reagent ion, and the quantitative curve is fitted by utilizing the secondary reaction kinetics, so that compared with the traditional linear fitting, the quantitative range of the sample to be detected is widened, and the quantitative accuracy and the detection repeatability of the ion mobility spectrometry are improved.
Description
Technical Field
The invention relates to a quantitative method for sample analysis, in particular to a quantitative method for sample detection by using ion mobility spectrometry.
Background
Ion Mobility Spectrometry (IMS) is an analysis technology for characterizing substances based on the migration velocity difference of gas-phase ions with different gases in an electric field, is increasingly applied to the fields of public safety, environmental monitoring, clinical diagnosis and the like due to the advantages of high detection speed, high sensitivity, low manufacturing cost, easiness in carrying and the like, but is influenced by various external conditions and the conditions of instruments, and the quantitative accuracy of the ion mobility spectrometry is limited. The ionization source improves the reactant ions, the reactant ions can react with a sample to be detected to realize ionization and detection of the object to be detected, the change of the signal intensity of the reagent ions can influence the change of the signal intensity of the sample to be detected, and the signal intensity of the reagent ions is influenced by many factors, for example, when the ionization source is a vacuum ultraviolet lamp, the attenuation of the lamp can cause the weakening of the signal intensity of the reagent ions, the unstable concentration of the reagent molecules can also cause the change of the signal intensity of the reagent ions, the change of the voltage applied to an electrode ring of the ion migration tube, the change of the flow rate of carrier gas drift and the like can influence the signal intensity of the reagent ions, and therefore, the accurate quantification of the object to be detected under different conditions is necessary.
The invention provides a quantitative method for sample detection by ion mobility spectrometry, which utilizes the ratio of the maximum signal intensity of a sample to be detected under different concentrations to the ion signal intensity of an initial reaction reagent to obtain the proportionality coefficient of the sample to be detected under different concentrations for quantifying the sample, and corrects the change of the sample signal intensity caused by the change of the ion signal intensity of the initial reaction reagent. The quantitative curve is fitted by utilizing the secondary reaction kinetics, compared with the traditional linear fitting, the quantitative range of the sample to be detected is widened, and the quantitative accuracy and the detection repeatability of the ion mobility spectrometry are improved.
Disclosure of Invention
Firstly, preparing more than 5 times of samples with different concentrations, then detecting the samples with different concentrations by using an ion mobility spectrometry, introducing reaction reagent molecules into a reaction area of the ion mobility spectrometry, then respectively detecting the samples with different concentrations by using the ion mobility spectrometry, recording the signal intensity of initial reaction reagent ions before sample introduction, dynamically tracking the signal intensity of sample product ions after sample introduction, obtaining the maximum signal intensity of the samples under the concentration, detecting the samples with each concentration for five times, comparing the maximum signal intensity of the sample product ions obtained each time with the signal intensity of the initial reaction reagent ions, obtaining the average proportionality coefficient of the samples under the concentration, and obtaining the average proportionality coefficient under the concentration by calculating the average value of the proportionality coefficients for more than five times; then the average proportional coefficient and the concentration are respectively used as horizontal and vertical coordinates, the average proportional coefficient of more than five samples with different concentrations is used for drawing a scatter diagram for the corresponding concentration, and a deduced secondary reaction kinetic formula is utilized
Fitting to obtain a standard curve of the sample, wherein a, b and c are fitting parameters, x is the concentration of the sample, and y is the proportionality coefficient of the sample under the concentration of x;
the concentration x of the sample is obtained by taking the proportionality coefficient y of the sample with unknown concentration (x) into a standard curve by the same sample injection method and conditions.
Only one reactant ion is ionized in the ion mobility spectrometry and can react with a substance to be detected, and only one product ion is generated, thereby meeting the requirement of a second-level reaction kinetic equation.
Detecting a sample by adopting an ion mobility spectrometry to obtain the migration time of the left edge and the right edge of the ion peak of the product of the sample, setting the migration time range by software, and tracking the change of the signal intensity of the product ion peak in the sample introduction process in the migration time range.
Ion mobility spectrometry can operate in positive or negative ion mode.
And in the samples with different concentrations, the same concentration needs to be subjected to five times of parallel tests, and the average value of the proportionality coefficients of the five times of parallel tests is used for fitting a standard curve equation.
The reaction reagent molecules can be acetone, butanone, benzene, toluene, anisole and other organic solvents with ionization energy less than 10.6eV and capable of being photoionized, and the inlet concentration is 1-30 ppm; the samples are traditional explosives such as TNT, PETN, AN and the like and novel peroxygenated explosives TATP and HMTD, drugs such as cocaine, codeine and morphine and the like, anesthetics such as propofol and sevoflurane, VOCs in exhaled breath such as ammonia, acetone and isoprene and the like.
The invention has the advantages that:
the method obtains the proportionality coefficient of the sample to be detected under different concentrations by utilizing the ratio of the maximum signal intensity of the sample to be detected under different concentrations to the initial reaction signal intensity, and compared with the traditional ion mobility spectrometry quantification method which utilizes the signal intensity of the sample to be detected under different concentrations to quantify, the quantification method is free from the change of the signal intensity of the sample to be detected caused by the change of the initial reaction reagent ion signal intensity, and the quantification accuracy of the sample to be detected is improved.
The quantitative curve is fitted by utilizing the secondary reaction kinetics, compared with the traditional linear fitting, the quantitative range of the sample to be detected is widened, and the quantitative accuracy and the detection repeatability of the ion mobility spectrometry are improved.
Drawings
FIG. 1 is a dynamic tracking curve of 5ppbv (100% RH) propofol product ion peak signal intensity and water molecule peak signal intensity during sample injection for 10 s;
FIG. 2 is a graph of the ratio of the maximum signal intensity of the 5ppbv (100% RH) propofol product ion peak to the signal intensity of the initial reagent ion at different initial reaction signal intensities;
FIG. 3 is a standard curve obtained by fitting a second order reaction kinetics equation to a plot of the ratio of maximum signal intensity of propofol to initial reagent ionic signal intensity versus concentration over a concentration range of 1-45 ppbv.
Detailed Description
The invention discloses a quantitative method for sample detection by using ion mobility spectrometry, which adopts reagent molecules to assist photoionization positive ion mobility spectrometry and combines a time-resolved dynamic dilution sampling device to detect propofol with different concentrations, thereby widening the quantitative range of propofol in exhaled breath and improving the quantitative accuracy and the detection repeatability.
The ion mobility spectrometry is operated in positive ion mode, and the reactive reagent ion C in the ion mobility spectrometry6H5CH3 +Reacting with Propofol sample to produce [ Propofol ] as product ion]+And meets the requirement of a two-stage reaction kinetic equation.
And (3) detecting the propofol sample by adopting an ion mobility spectrometry to obtain the migration time of the left edge and the right edge of the propofol product ion peak, setting the migration time range 9200-10200us by software, and tracking the change of the signal intensity in the sample introduction process of the product ion peak.
Accurately prepared 100% RH propofol samples at concentrations of 1.6ppbv, 2.1ppbv, 2.8ppbv, 3.3ppbv, 4.1ppbv, 5.5ppbv, 6.6ppbv, 8.1ppbv, 10.8ppbv, 13.4ppbv, 14.5ppbv, 27.2ppbv, 35.7ppbv and 44.0ppbv, respectively, ion mobility spectrometry was carried out under experimental conditions of a migration tube of 90 ℃, sample carrier gas flow rate and drift gas flow rate of 500ml/min and 200ml/min, respectively, sampling time of 20s and sample introduction time of 10 s. Five replicates of each concentration sample were run in parallel.
Recording the signal intensity of initial reaction reagent ions before sample introduction, dynamically tracking the signal intensity of sample product ions in a specific migration time range after sample introduction, and obtaining the maximum signal intensity of the sample under the concentration, wherein each signal intensity isDetecting a sample with concentration five times, comparing the maximum signal intensity of the sample product ions obtained each time with the signal intensity of the initial reaction reagent ions to obtain an average proportionality coefficient of the sample under the concentration, calculating the average value of the quintic proportionality coefficient under the concentration to obtain the average proportionality coefficient under the concentration, then respectively taking the average proportionality coefficient and the concentration as horizontal and vertical coordinates, drawing a scatter diagram of the average proportionality coefficients of samples with different concentrations more than five times to the corresponding concentrations, and utilizing a deduced secondary reaction kinetic formula
Fitting to obtain a standard curve of the sample, wherein a, b and c are fitting parameters, x is the concentration of the sample, and y is the proportionality coefficient of the sample under the concentration of x; the concentration x of the sample is obtained by taking the proportionality coefficient y of the sample with unknown concentration (x) measured under the same sample injection method and conditions into a standard curve.
Example 1
The ion mobility spectrometry is operated in positive ion mode, and the reactive reagent ion C in the ion mobility spectrometry6H5CH3 +Reacting with Propofol sample to produce [ Propofol ] as product ion]+And meets the requirement of a two-stage reaction kinetic equation. The experimental conditions of the ion mobility spectrometry are that the migration tube is 90 ℃, the flow rate of the sample carrier gas and the flow rate of the floating gas are respectively 500ml/min and 200ml/min, the sampling time is 20s, and the sample injection time is 10 s. Preparing a 5ppbv 100% RH propofol sample, detecting the propofol sample by adopting ion mobility spectrometry to obtain the migration time of the left edge and the right edge of the propofol product ion peak, setting the migration time range 9200-10200us by software, and tracking the change of signal intensity in the sample introduction process of the product ion peak. And tracking the ion peak of the propofol product and the water molecule peak 1 and peak 2 in the continuous sample injection process for 10s to obtain a dynamic tracking curve shown in figure 1, obtaining the maximum signal intensity of the sample injection 4s propofol, comparing the maximum signal intensity with the recorded initial reaction reagent ion signal intensity (RIP) to obtain a proportionality coefficient under the concentration, and performing five times of repeated experiments in parallel to obtain an average proportionality coefficient under the concentration.
Example 2
The ion mobility spectrometry is operated in positive ion mode, and the reactive reagent ion C in the ion mobility spectrometry6H5CH3 +Reacting with Propofol sample to produce [ Propofol ] as product ion]+And meets the requirement of a two-stage reaction kinetic equation. The experimental conditions of the ion mobility spectrometry are that the migration tube is 90 ℃, the flow rate of the sample carrier gas and the flow rate of the floating gas are respectively 500ml/min and 200ml/min, the sampling time is 20s, and the sample injection time is 10 s. Preparing a 5ppbv 100% RH propofol sample, detecting the propofol sample by adopting ion mobility spectrometry to obtain the migration time of the left edge and the right edge of the propofol product ion peak, setting the migration time range 9200-10200us by software, tracking the change of signal intensity in the sample injection process of the product ion peak, and performing five times of repeated experiments in parallel. Under different initial reagent ion signal intensities (RIP), 5ppbv 00% RH propofol is detected, and the result is that as shown in FIG. 2, the ratio of the signal intensity of propofol to the initial reagent ion signal intensity does not change with the initial reagent ion signal intensity, so the ratio of the signal intensity of propofol with a fixed concentration to the RIP intensity is not affected by the RIP intensity in the exhaled breath detection process.
Example 3
The ion mobility spectrometry is operated in positive ion mode, and the reactive reagent ion C in the ion mobility spectrometry6H5CH3 +Reacting with Propofol sample to produce [ Propofol ] as product ion]+And meets the requirement of a two-stage reaction kinetic equation. The experimental conditions of the ion mobility spectrometry are that the migration tube is 90 ℃, the flow rate of the sample carrier gas and the flow rate of the floating gas are respectively 500ml/min and 200ml/min, the sampling time is 20s, the sample injection time is 10s, and five times of repeated experiments are carried out on samples under each concentration in parallel. Under a certain initial Reagent Ion (RIP) signal intensity, 100% RH propofol samples prepared at 1.6ppbv, 2.1ppbv, 2.8ppbv, 3.3ppbv, 4.1ppbv, 5.5ppbv, 6.6ppbv, 8.1ppbv, 10.8ppbv, 13.4ppbv, 14.5ppbv, 27.2ppbv, 35.7ppbv and 44.0ppbv are detected, and the ratio of the maximum signal intensity of propofol to the initial reagent ion signal intensity, namely the proportionality coefficient, is changed along with the propofol concentration. According to the second order of reactionBy applying a kinetic formula, the functional relation between the two is deduced
The origin software is used for carrying out fitting to obtain a standard curve of the propofol, wherein the parameter a is 14.78, the parameter b is 0.07, the parameter c is 0.55, and the standard curve equation is
Coefficient of correlation R20.99, the quantitative range is 0.2-45ppbv, and the detection limit (S/N-3) is 26 pptv.
Claims (6)
1. A quantitative method for sample detection by ion mobility spectrometry is characterized in that: firstly, preparing more than five samples with different concentrations, introducing reaction reagent molecules into a reaction area of an ion mobility spectrum, then respectively detecting the samples with different concentrations by using the ion mobility spectrum, recording the signal intensity of initial reaction reagent ions before sample introduction, dynamically tracking the signal intensity of sample product ion peaks after sample introduction, obtaining the maximum signal intensity of the samples under the concentration, detecting the samples with each concentration for more than five times, comparing the maximum signal intensity of the sample product ions obtained each time with the signal intensity of the initial reaction reagent ions to obtain the proportionality coefficient of the samples under the concentration, and calculating the average value of the proportionality coefficients for more than five times to obtain the average proportionality coefficient under the concentration; then the average proportional coefficient and the concentration are respectively used as horizontal and vertical coordinates, the average proportional coefficient of more than five samples with different concentrations is used for drawing a scatter diagram for the corresponding concentration, and a deduced secondary reaction kinetic formula is utilized
Fitting to obtain a standard curve of the sample;
adopting the same sample introduction method and conditions of the samples to measure the proportionality coefficient y of the samples with unknown concentration to be substituted into a standard curve to obtain the concentration x of the samples with unknown concentration, wherein a, b and c are parameters needing fitting;
only one reactant ion is ionized in the ion mobility spectrometry, and the reactant ion can react with a substance to be detected, only one product ion is generated, and the requirement of a second-level reaction kinetic equation is met.
2. The method of claim 1, wherein: detecting a sample to be detected by adopting an ion mobility spectrometry to obtain the migration time of the left edge and the right edge of the ion peak of the product of the sample, setting the migration time range through software, and tracking the change of signal intensity of the product ion peak in the sample introduction process in the migration time range.
3. The method of claim 1, wherein: ion mobility spectrometry operates in either positive or negative ion mode.
4. The method of claim 1, wherein: and in the samples with different concentrations, the same concentration needs to be subjected to five times of parallel tests, and the average value of the proportionality coefficients of the five times of parallel tests is used for fitting a standard curve equation.
5. The method of claim 1, wherein:
the reaction reagent molecules can be acetone, butanone, benzene, toluene and organic solvent with ionization energy less than 10.6eV and capable of being photoionized, and the introduced concentration is 1-30 ppm; the samples were VOCs in conventional explosives, novel peroxygenated explosives, drugs, narcotics or exhaled breath.
6. The method of claim 5, wherein:
the traditional explosive is TNT, PETN or AN; the novel peroxide explosive is TATP and HMTD; the narcotics are propofol, codeine and morphine, and the narcotics are propofol and sevoflurane; the VOCs in the exhaled breath are ammonia, acetone and isoprene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711161879.8A CN109813792B (en) | 2017-11-21 | 2017-11-21 | Quantitative method for sample detection by using ion mobility spectrometry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711161879.8A CN109813792B (en) | 2017-11-21 | 2017-11-21 | Quantitative method for sample detection by using ion mobility spectrometry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109813792A CN109813792A (en) | 2019-05-28 |
| CN109813792B true CN109813792B (en) | 2021-07-27 |
Family
ID=66599523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711161879.8A Active CN109813792B (en) | 2017-11-21 | 2017-11-21 | Quantitative method for sample detection by using ion mobility spectrometry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109813792B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112924521A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Real-time online ion mobility spectrometry quantification method |
| CN117503106A (en) * | 2023-11-27 | 2024-02-06 | 苏州邦伊医疗科技有限公司 | Dynamic correlation coefficient detection system for propofol concentration and blood concentration in exhaled breath |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103877645A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Detection control device for anesthetics in blood |
| CN105628783A (en) * | 2014-10-28 | 2016-06-01 | 中国科学院大连化学物理研究所 | Application of reagent molecules in ion mobility spectrometry detection of explosive peroxide HMTD |
| CN106198704B (en) * | 2015-05-06 | 2018-12-07 | 中国科学院大连化学物理研究所 | A kind of quantitative analysis method for ion mobility spectrometry |
| US20170213715A1 (en) * | 2015-12-18 | 2017-07-27 | Morpho Detection, Llc | Detection of compounds through dopant-assisted photoionization |
-
2017
- 2017-11-21 CN CN201711161879.8A patent/CN109813792B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109813792A (en) | 2019-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Puton et al. | Ion mobility spectrometry: Current status and application for chemical warfare agents detection | |
| CN108072690B (en) | Ion mobility spectrometry and ion trap mass spectrometry combined device and analysis method | |
| CN106226384B (en) | A kind of trimethylamine detection method based on Ion mobility spectrometry | |
| EP3011585A1 (en) | Method and device for ionizing particles of a sample gas flow | |
| Zalewska et al. | Limits of detection of explosives as determined with IMS and field asymmetric IMS vapour detectors | |
| CN101413919A (en) | Method for recognizing and analyzing sample and ion transfer spectrometer | |
| Wolf et al. | Determination of chromium and beryllium at the picogram level by gas chromatography-mass spectrometry | |
| Xie et al. | Determination of acetone, 2-butanone, diethyl ketone and BTX using HSCC-UV-IMS | |
| CN104713945A (en) | Method for detecting explosive peroxide TATP | |
| CN109813792B (en) | Quantitative method for sample detection by using ion mobility spectrometry | |
| CN108072689A (en) | A kind of quantitative analysis method for ion mobility spectrometry | |
| Urabe et al. | Development of portable mass spectrometer with electron cyclotron resonance ion source for detection of chemical warfare agents in air | |
| CN109813798B (en) | Method for continuously monitoring hazardous chemical substances on line or rapidly identifying leaked substances | |
| CN111443125A (en) | Correction method for detecting hazardous substance residues by using ion mobility spectrometry | |
| US7956323B2 (en) | Ion mobility spectrometer and method for determining an analyte substance or an analyte substance mixture in the presence of a dopant mixture by means of an ion mobility spectrometer | |
| CN112611798B (en) | Online mass spectrum detection method for isomers | |
| Han et al. | Determination of alcohol compounds using corona discharge ion mobility spectrometry | |
| CN108008001A (en) | Improve three peroxidating diamines of hexa-methylene（HMTD）The detection method of dosing accuracy | |
| CN101169389A (en) | Method for quickly determining trinitrotoluene or hexogen in solution | |
| Liao et al. | Rapid measurement of Phthalic acid Ester environmental hormones using ion mobility spectrometry | |
| RU2277238C2 (en) | Method of measurement of concentration of impurities in nitrogen, hydrogen and oxygen by means of ion mobility spectrometry | |
| Wang et al. | Control of solvent use in medical devices by proton transfer reaction mass spectrometry and ion molecule reaction mass spectrometry | |
| Vautz et al. | Sensitive ion mobility spectrometry of humid ambient air using 10.6 eV UV-IMS | |
| Takahashi et al. | Detection and measurement of S-benzyl-N-acetylcysteine in urine of toluene sniffers using capillary gas chromatography | |
| Pedersen et al. | Characterization of proton-bound acetate dimers in ion mobility spectrometry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |